甲烷/氧化亚氮绿色推进剂自着火特性实验及动力学

doi:10.11949/0438-1157.20240799

摘要/Abstract

摘要：

利用加热的快速压缩机研究了氩气稀释下甲烷/氧化亚氮（CH₄/N₂O/Ar）推进剂的自着火特性，使用压力传感器和光信号采集系统同步获得了推进剂自着火过程压力及光信号强度；实验观察到了区分着火和不着火现象的临界着火条件，使用着火延迟期对推进剂的反应活性进行了分析；利用动力学模型对CH₄/N₂O/Ar在中低温下的着火微观反应过程进行模拟和分析。结果表明：CH₄/N₂O/Ar混合气临界着火温度随着压力和推进剂浓度的增加而降低；CH₄/N₂O/Ar混合气的着火延迟期随着温度及压力的增加而缩短。杨模型能够在全温度压力范围内对混合气的着火延迟期进行较好的预测。其着火过程中CH₄主要通过H提取反应消耗，而N₂O主要通过分解反应及N₂O + H $̿$ N₂ + OH反应消耗。

关键词: 氧化亚氮, 碳氢化合物, 快速压缩机, 临界着火条件, 着火延迟期, 反应动力学

Abstract:

Nitrous oxide and fuel blend (NOFBX) has been considered as potential hydrazine replacement due to their advantages of non-toxic, high-performance, and low-cost as monopropellant. The methane and nitrous oxide (CH₄/N₂O), a typical NOFBX combination, provides significant benefits for meeting propulsion performances and has become a focus of increased research in recent years. In addition, N₂O and CH₄ can be stored in one premixed tank, which would increase the risk of ignition of premixed fuel and oxidizer at high self-pressurized condition. However, limited data has been published on the ignition safety and ignition delay time (IDT) of CH₄/N₂O at high pressure, resulting in unclear understanding of the ignition hazards and mechanisms. In this work, the ignition behaviors of Ar diluted CH₄/N₂O were experimentally investigated firstly in a heated rapid compression machine (RCM) by detecting the pressure and light emission traces at temperatures and pressures ranging from 1125—1450 K and 10—40 bar. The critical ignition temperature which separates the non-ignition and ignition cases was determined. The results show that the critical ignition temperature decreases with the increases of pressure and fuel/oxidizer concentration. For the successful ignition cases, the ignition delay times were measured and used to validate several recently developed kinetic mechanisms. The results show that the IDT predictions from Yang model have good agreement with the measured IDTs. During the ignition process, CH₄ is mainly consumed by H extraction reaction, while N₂O is mainly consumed by decomposition reaction and reaction N₂O + H $̿$ N₂ + OH.

Key words: nitrous oxide, hydrocarbons, rapid compression machine, critical ignition condition, ignition delay time, reaction kinetics

中图分类号:

V 11

杨猛, 丁晓倩, 余涛, 刘畅, 汤成龙, 黄佐华. 甲烷/氧化亚氮绿色推进剂自着火特性实验及动力学[J]. 化工学报, 2025, 76(3): 1221-1229.

Meng YANG, Xiaoqian DING, Tao YU, Chang LIU, Chenglong TANG, Zuohua HUANG. Experimental and kinetic studies for the ignition characteristic of the green propellant of methane/nitrous oxide[J]. CIESC Journal, 2025, 76(3): 1221-1229.

图/表 9

图1 快速压缩机装置图

Fig.1 The schematic of the rapid compression machine

表1 测试工况和反应物组分

Table 1 Test conditions and reactant mixtures

Mix	CH₄/N₂O	体积分数/%			p_c/bar
Mix	CH₄/N₂O	CH₄	N₂O	Ar	p_c/bar
1	1/4	1	4	95	10、15、20、25、30、35、40
2	1/4	2	8	90	10、15、20、25、30、35、40

图2 RCM典型的压力、光信号曲线以及IDT定义

Fig.2 Typical pressure and light intensity traces and IDT definition of the RCM

图3 不同工况下着火测试点、着火区域以及拟合的临界着火边界

Fig.3 Test points and regions about ignition at different conditions and the fitting of critical ignition limit

图4 CH4/N2O/Ar混合气实验和模拟的着火延迟期

Fig.4 Experimental and simulated ignition delay times of CH4/N2O/Ar

图5 实验、拟合与模拟的临界着火边界对比

Fig.5 Comparisons of the experimental, fitted and simulated auto-ignition boundary

图6 30 bar和1200 K条件下与甲烷和氧化亚氮生成速率相关的主要基元反应

Fig.6 Rates of production of methane and nitrous oxide through the main elementary reactions at 30 bar and 1200 K

表2 1%CH4/4%N2O/95%Ar混合气在着火过程中主要的甲烷和氧化亚氮生成与消耗相关的基元反应

Table 2 Main elementary reactions related to the formation and consumption of methane and nitrous oxide in the ignition processes of 1%CH4/4%N2O/95%Ar mixture

Species	Number	Elementary reaction
methane	R43	CH₃ + H (+M) $̿$ CH₄ (+M)
	R44	CH₄ + H $̿$ CH₃ + H₂
	R45	CH₄ + O $̿$ CH₃ + OH
	R46	CH₄ + OH $̿$ CH₃ + H₂O
	R158	CH₂O + CH₃ $̿$ HCO + CH₄
	R203	C₂H₆ + CH₃ $̿$ C₂H₅ + CH₄
nitrous oxide	R994	N₂O (+M) $̿$ N₂ + O (+M)
	R995	N₂O + H $̿$ N₂ + OH
	R1004	N₂O + H₂ $̿$ N₂ + H₂O
	R1083	NH + NO $̿$ N₂O + H
	R1240	HCO + NO $̿$ HNO + CO

表2 1%CH4/4%N2O/95%Ar混合气在着火过程中主要的甲烷和氧化亚氮生成与消耗相关的基元反应

Table 2 Main elementary reactions related to the formation and consumption of methane and nitrous oxide in the ignition processes of 1%CH4/4%N2O/95%Ar mixture

Species	Number	Elementary reaction
methane	R43	CH₃ + H (+M) $̿$ CH₄ (+M)
	R44	CH₄ + H $̿$ CH₃ + H₂
	R45	CH₄ + O $̿$ CH₃ + OH
	R46	CH₄ + OH $̿$ CH₃ + H₂O
	R158	CH₂O + CH₃ $̿$ HCO + CH₄
	R203	C₂H₆ + CH₃ $̿$ C₂H₅ + CH₄
nitrous oxide	R994	N₂O (+M) $̿$ N₂ + O (+M)
	R995	N₂O + H $̿$ N₂ + OH
	R1004	N₂O + H₂ $̿$ N₂ + H₂O
	R1083	NH + NO $̿$ N₂O + H
	R1240	HCO + NO $̿$ HNO + CO

图7 在1200 K和30 bar条件下CH4/N2O/Ar混合气反应路径分析(CH4的消耗为20%)

Fig.7 Reaction pathway analyses at 20% CH4 consumption for CH4/N2O/Ar at 1200 K and 30 bar

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